Mixture for liquid crystal medium and liquid crystal display using the same

ABSTRACT

The present invention provides a mixture for liquid crystal medium and a liquid crystal display using the same. The mixture for liquid crystal medium comprises: at least one anisotropic liquid crystal material and two or more polymerizable monomers which will polymerize under UV irradiation. The liquid crystal material comprises an alkenyl compound which is stable to the polymerization reaction during the polymerization of the polymerizable monomers. The weight percentage of the polymerizable monomers accounts for 0.1% to 1% of the total mixture for liquid crystal medium. In the mixture for liquid crystal medium and a liquid crystal display using the same according to the present invention, by using two or more polymerizable monomers which will polymerize under UV irradiation and the appropriate content ratio, the polymer bump with small size and good uniformity can be obtained within the mixture for liquid crystal medium after the polymerization, which avoids the bad liquid crystal alignment and the light spot occurred at the dark state of the liquid crystal panel, and then increases the response rapid of the liquid crystal panel to obtain high contrast ratio and stable mass production.

This application claims priority to Chinese Patent Application SerialNo. 201210360734.1, named as “mixture for liquid crystal medium andliquid crystal display using the same”, filed on Sep. 21, 2012, thespecification of which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the field of liquid crystal displaytechnology, and in particular to a mixture for liquid crystal medium anda liquid crystal display using the same.

2. The Related Arts

The liquid crystal used for twisted nematic (TN) or super twistednematic (STN) liquid crystal display is positive-type liquid crystal.The long axis of the liquid crystal molecules is parallel to the surfaceof the substrate when the power is off. The alignment direction of theliquid crystal molecules on the surface of the substrate depends on therubbing direction of alignment layer, which material usually ispolyimide. The alignment directions of the surface of both substratesare perpendicular to each other. Hence, the molecules within the liquidcrystal layer maintain in continuous twisted alignment state from thesurface of one substrate to the surface of the other substrate. Afterthe voltage is applied, the long axis of the liquid crystal moleculeswill tend to be aligned along the direction of the electric field. Thedrawback of the TN/STN type liquid crystal display is that it has smallviewing angle, brightness difference and significant chromaticaberration under large viewing angle, which needs to be improved by thecompensation film and thereby increases the manufacturing cost of thedisplay.

Multi-domain vertical alignment (MVA) TFT-LCD using negative type liquidcrystal and vertically aligned film material has solved the restrictionsof the viewing angle of TN/STN display. When no voltage is applied, thelong axis of the liquid crystal molecules is perpendicular to thesurface of the substrate. When the voltage is applied, the liquidcrystal molecules will topple down and the long axis of the liquidcrystal molecules will tend to be aligned along the vertical directionof the electric field. In order to solve the problems of the viewingangle, a sub-pixel is divided into multiple regions, so that the liquidcrystal molecules can topple down in different direction, which makesthe views of the display seen in different directions tend to be thesame. There are several ways to allow the liquid crystal molecules inthe different regions to be oriented in different directions in onesub-pixel. The first one is to build a bump at the upper and lowersubstrates of the LCD by exposure and development, so that the liquidcrystal molecules around the bump can produce a certain pre-inclinedangle and topple down toward the fixed direction. The second one is toform predetermined pattern of indium tin oxide (ITO) pixel electrodes atthe upper and lower substrates, which will generate an electric fieldwith a certain inclined angle to control the toppling direction of theliquid crystal molecules in the different regions. This is called aspatterned vertical alignment (PVA) technology. The third one is to formITO slits at the TFT side of the LCD substrate and full ITO at the otherside. And then add the polymerizable monomer into the liquid crystalmedium. First, make the liquid crystal molecules topple down by anelectric field, at the same time, irradiate the monomer with ultravioletlight to polymerize and form the polymer particles which can guide thetoppling direction of the liquid crystal molecules. The polymerparticles deposited on the surface of the substrate play the role of thealignment. This is called as polymer stabilized vertical alignment(PSVA).

The reaction rate of the polymerizable monomer, the size and thedistribution of the polymer, the surface uniformity of the substrate,and the strength of the alignment force have major impacts on theoptical properties of the panel and the stability of the production. Inaddition to the process conditions, these factors are mainly dependenton the molecular structure of the polymerizable monomer which directlydetermines the speed of the light reaction, the characteristics of thepolymer and the strength of the alignment force to the liquid crystal.Because the conventional liquid crystal medium comprises alkenylcompound, it is beneficial to obtain a low rotational viscosity toimprove the response of liquid crystal medium. The alkenyl compoundwithin the liquid crystal medium will affect the polymerization reactionof the polymerizable monomer easily and then the alignment of the liquidcrystal medium. Hence, in general, single polymerizable monomer is verydifficult to make the factors mentioned above in a favorable situation.The actual situation often attends to one thing and loses track ofanother, such as good uniformity of the polymer accompanied with lowalignment force, or strong alignment force accompanied with slowreaction rate and so on.

SUMMARY OF THE INVENTION

The technical issue to be solved by the present invention is to providea mixture for liquid crystal medium, wherein by using two or morepolymerizable monomers with different functions, the reaction rate ofthe polymerization reaction, the uniformity of the generated polymer andthe strength of the alignment force can be balanced at the same time andreach a higher level.

The present invention further provides a liquid crystal displaycomprising the mixture for liquid crystal medium, wherein by using twoor more polymerizable monomers with different functions, the reactionrate of the polymerization reaction of the monomer, the uniformity ofthe generated polymer and the strength of the alignment force can bebalanced at the same time and reach a higher level, which improves theoptical properties and overall performance of the panel and the stablemass production.

In order to solve the technical issue, the embodiment according to thepresent invention provides a mixture for liquid crystal mediumcomprising: at least one anisotropic liquid crystal material and two ormore polymerizable monomers which will polymerize under UV irradiation,the liquid crystal material comprising an alkenyl compound which isstable to the polymerization reaction during the polymerization of thepolymerizable monomers, the weight percentage of the polymerizablemonomers accounting for 0.1% to 1% of the total mixture for liquidcrystal medium; the structural formulas of the two or more polymerizablemonomers defined by at least one of the following structural formulas,the number of groups is different when the structural formulas of thetwo or more polymerizable monomers are the same:

wherein, in formula I to IV, P represents the polymerizable group, whichis selected from the group consisting of a methacrylate group, anacrylate group, a vinyl group, an ethylene group, and an epoxy group; nrepresents the number of the polymerizable groups Ps connected to thesame aromatic ring, n represents an integer from 1 to 3, if n is greaterthan 1, the polymerizable groups may be the same or different, whereinthe polymerizable groups in formula I to IV are all methacrylate groupwhen the polymerizable groups are different;X represents substituent group, which is selected from the groupconsisting of —F, —Cl, —Br, methyl, —CN, and straight chain or branchedchain alkyl containing number of carbon atoms from 2 to 8, one or morenon-adjacent methyl groups of the alkyl may be replaced by oxygen orsulfur atom; m represents the number of the substituent groups connectedto the same aromatic ring, m represents an integer from 1 to 3, if m isgreater than 1, the substituent groups may be the same or different;in formula IV, Z is selected from the group consisting of —O—, —COO—,—OCO—, —CH₂O—, —OCH₂O—, —O(CH₂)₂O—, —COCH₂—, methylene, —C≡C—,

Wherein, any hydrogen on the aromatic ring in the structural formulas ofthe polymerizable monomer may be substituted by the group of —F, —Cl,—Br, methyl or —CN.

Wherein, any hydrogen not on the aromatic ring in the structuralformulas of the polymerizable monomer may be substituted by the group of—F, —Cl, —Br or methyl.

Wherein, the two polymerizable monomers respectively are as follows:

the molar ratio of the two polymerizable monomers in the mixture forliquid crystal medium is 1:5.

Wherein, the alkenyl compound defined by the following structuralformulas:

wherein,

independently represents:

R1 represents the straight chain or branched chain alkenyl containingnumber of carbon atoms from 2 to 9;R2 represents the straight chain or branched chain alkyl containingnumber of carbon atoms from 1 to 12;X independently represents H

F

Cl

OCF₃ or CF₃;m represents from 1 to 4;n and k respectively represents from 0 to 3.

The embodiment according to the present invention further provides aliquid crystal display comprising: a upper substrate and a lowersubstrate which are parallel with each other, and a mixture for liquidcrystal medium provided between the upper substrate and the lowersubstrate, the mixture for liquid crystal medium comprising: at leastone anisotropic liquid crystal material and two or more polymerizablemonomers which will polymerize under UV irradiation, the liquid crystalmaterial comprising an alkenyl compound which is stable to thepolymerization reaction during the polymerization of the polymerizablemonomers, the weight percentage of the polymerizable monomers accountingfor 0.1% to 1% of the total mixture for liquid crystal medium; thestructural formulas of the two or more polymerizable monomers defined byat least one of the following structural formulas, the number of groupsis different when the structural formulas of the two or morepolymerizable monomers are the same:

wherein, in formula I to IV, P represents the polymerizable group, whichis selected from the group consisting of a methacrylate group, anacrylate group, a vinyl group, an ethylene group, and an epoxy group; nrepresents the number of the polymerizable groups Ps connected to thesame aromatic ring, n represents an integer from 1 to 3, if n is greaterthan 1, the polymerizable groups may be the same or different, whereinthe polymerizable groups in formula I to IV are all methacrylate groupwhen the polymerizable groups are different;X represents substituent group, which is selected from the groupconsisting of —F, —Cl, —Br, methyl, —CN, and straight chain or branchedchain alkyl containing number of carbon atoms from 2 to 8, one or morenon-adjacent methyl groups of the alkyl may be replaced by oxygen orsulfur atom; m represents the number of the substituent groups connectedto the same aromatic ring, m represents an integer from 1 to 3, if m isgreater than 1, the substituent groups may be the same or different;in formula IV, Z is selected from the group consisting of —O—, —COO—,—OCO—, —CH₂O—, —OCH₂O—, —O(CH₂)₂O—, —COCH₂—, methylene, —C≡C—,

Wherein, any hydrogen on the aromatic ring in the structural formulas ofthe polymerizable monomer may be substituted by the group of —F, —Cl,—Br, methyl or —CN.

Wherein, any hydrogen not on the aromatic ring in the structuralformulas of the polymerizable monomer may be substituted by the group of—F, —Cl, —Br or methyl.

Wherein, the two polymerizable monomers respectively are as follows:

the molar ratio of the two polymerizable monomers in the mixture forliquid crystal medium is 1:5.

Wherein, the alkenyl compound defined by the following structuralformulas:

wherein,

independently represents:

R1 represents the straight chain or branched chain alkenyl containingnumber of carbon atoms from 2 to 9;R2 represents the straight chain or branched chain alkyl containingnumber of carbon atoms from 1 to 12;X independently represents H

F

Cl

OCF₃ or CF₃;m represents from 1 to 4;n and k respectively represents from 0 to 3.

The embodiment according to the present invention has the beneficialeffects as follow:

the mixture for liquid crystal medium according to the presentinvention, by using two or more polymerizable monomers which willpolymerize under UV irradiation and the appropriate content ratio, thepolymer bump with small size and good uniformity can be obtained afterthe polymerization, which avoids the bad liquid crystal alignment andthe light spot occurred at the dark state of the liquid crystal panel,and then increases the response rapid of the liquid crystal panel toobtain high contrast ratio. It improves the optical properties andoverall performance of the panel and the stable mass production whenapplied in the liquid crystal display.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In order to further illustrate technical means and effects thereofaccording to the present invention, the accompanying drawings and thefollowing detailed descriptions are the preferred embodiments of thepresent invention.

The present invention provides a mixture for liquid crystal medium usedfor liquid crystal display. The mixture for liquid crystal mediumcomprises: at least one anisotropic liquid crystal material and two ormore polymerizable monomers which will polymerize under UV irradiation.The liquid crystal material comprises an alkenyl compound which isstable to the polymerization reaction during the polymerization of thepolymerizable monomers, the weight percentage of the polymerizablemonomers accounting for 0.1% to 1% of the total mixture for liquidcrystal medium. The structural formulas of the polymerizable monomersare composed of single benzene ring, two benzene rings or singlenaphthalene ring. The structure comprising two benzene rings is formedby two benzene rings connected directly or indirectly connected througha group with each other. The benzene ring and the naphthalene ring aredirectly connected with at least one polymerizable group.

The structural formulas of the two or more polymerizable monomers aredefined by at least one of the following structural formulas. The numberof groups is different when the structural formulas of the two or morepolymerizable monomers are the same:

wherein, in formula I to IV, P represents the polymerizable group, whichis selected from the group consisting of a methacrylate group, anacrylate group, a vinyl group, an ethylene group, and an epoxy group; nrepresents the number of the polymerizable groups Ps connected to thesame aromatic ring, n represents an integer from 1 to 3, if n is greaterthan 1, the polymerizable groups may be the same or different, whereinthe polymerizable groups in formula I to IV are all methacrylate groupwhen the polymerizable groups are different;X represents substituent group, which is selected from the groupconsisting of —F, —Cl, —Br, methyl, —CN, and straight chain or branchedchain alkyl containing number of carbon atoms from 2 to 8, one or morenon-adjacent methyl groups of the alkyl may be replaced by oxygen orsulfur atom; m represents the number of the substituent groups connectedto the same aromatic ring, m represents an integer from 1 to 3, if m isgreater than 1, the substituent groups may be the same or different;in formula IV, Z is selected from the group consisting of —O—, —COO—,—OCO—, —CH₂O—, —OCH₂O—, —O(CH₂)₂O—, —COCH₂—, methylene, —C≡C—,

Any hydrogen on the aromatic ring in the structural formulas of thepolymerizable monomer may be substituted by the group of —F, —Cl, —Br,methyl or —CN.

Any hydrogen not on the aromatic ring in the structural formulas of thepolymerizable monomer may be substituted by the group of —F, —Cl, —Br ormethyl.

The alkenyl compound defined by the following structural formulas:

wherein,

independently represents:

R1 represents the straight chain or branched chain alkenyl containingnumber of carbon atoms from 2 to 9;R2 represents the straight chain or branched chain alkyl containingnumber of carbon atoms from 1 to 12;X independently represents H

F

Cl

OCF₃ or CF₃;m represents from 1 to 4;n and k respectively represents from 0 to 3.

The two polymerizable monomers respectively are as follows:

the molar ratio of the two polymerizable monomers in the mixture forliquid crystal medium is 1:5.

The least one anisotropic liquid crystal material specifically is:

wherein, R represents the straight chain or branched chain alkylcontaining number of carbon atoms from 1 to 9, one or more non-adjacentmethyl groups or methylene groups of the alkyl may be replaced by oxygenor sulfur atom; the weight percentage of the anisotropic liquid crystalmaterial accounts for 20% to 90% of the total mixture for liquid crystalmedium.

The preferred embodiment according to the present invention is describedas follows.

Embodiment 1

The mixture for liquid crystal medium is chosen from negative-typeliquid crystal material and two kinds of polymerizable monomers asfollows:

The structural formula of the negative-type liquid crystal material is

The structural formulas of the two kinds of polymerizable monomers areRM-A1, RM-B1, and RM-A1 as follows:

The structural formulas of the RM-B1 is as follows:

The molar ratio of RM-A1 to RM-B1 is 1:5, which the total contentaccounts for 3000 ppm of the liquid crystal medium layer. In the mixturefor liquid crystal medium, the polymer bump, formed by mixing with RM-A1and RM-B1 after ultraviolet irradiation, has small and uniform size, andthe light spots won't occur at the dark state.

Embodiment 2

The mixture for liquid crystal medium is chosen from negative-typeliquid crystal material and two kinds of polymerizable monomers asfollows:

The structural formula of the negative-type liquid crystal material is

the structural formulas of the two kinds of polymerizable monomers areRM-A1, RM-B1, and RM-A1 as follows:

the structural formulas of the RM-B1 is as follows:

The molar ratio of RM-A1 to RM-B1 is 1:5, which the total contentaccounts for 1000 ppm of the liquid crystal medium layer. In the mixturefor liquid crystal medium, the polymer bump, formed by mixing with RM-A1and RM-B1 after ultraviolet irradiation, has small and uniform size, andthe light spots won't occur at the dark state.

Embodiment 3

The mixture for liquid crystal medium is chosen from negative-typeliquid crystal material and two kinds of polymerizable monomers asfollows:

The structural formula of the negative-type liquid crystal material is

the structural formulas of the two kinds of polymerizable monomers areRM-A1, RM-B1, and RM-A1 as follows:

the structural formulas of the RM-B1 is as follows:

The molar ratio of RM-A1 to RM-B1 is 1:5, which the total contentaccounts for 10000 ppm of the liquid crystal medium layer. In themixture for liquid crystal medium, the polymer bump, formed by mixingwith RM-A1 and RM-B1 after ultraviolet irradiation, has small anduniform size, and the light spots won't occur at the dark state.

In summary, the mixture for liquid crystal medium used for liquidcrystal display according to the present invention, by using two or morepolymerizable monomers which will polymerize under UV irradiation andthe appropriate content ratio, can control the size and the uniformityof the polymer bump formed by polymerization, which avoids the badliquid crystal alignment and the light spot occurred at the dark stateof the liquid crystal panel, and then obtains good optical performanceof the liquid crystal panel, such as high contrast ratio and highresponse speed.

The mixture for liquid crystal medium according to the present inventioncan be applied in display. The liquid crystal display according to thepresent invention uses the mixture for liquid crystal medium mentionedabove, which comprises a upper substrate and a lower substrate which areparallel with each other, and a mixture for liquid crystal mediumprovided between the upper substrate and the lower substrate. Themixture for liquid crystal medium is the mixture for liquid crystalmedium according to the present invention mentioned above and not berepeated here. By using the polymerizable monomers with differentfunctions in the mixture for liquid crystal medium, the reaction rate ofthe polymerization reaction, the uniformity of the generated polymer andthe strength of the alignment force can be balanced at the same time andreach a higher level. That is, while the reaction rate is quick, theuniformity of the generated polymer and the strength of the alignmentforce are also high, which improves the optical properties and overallperformance of the panel and the stable mass production.

It is to be understood that many other possible modifications andvariations can be made by those skilled in the art without departingfrom the spirit and scope of the invention as hereinafter claimed, andthose modifications and variations are considered encompassed in thescope of protection defined by the claims of the present invention.

What is claimed is:
 1. A mixture for liquid crystal medium comprising:at least one anisotropic liquid crystal material and two polymerizablemonomers which will polymerize under UV irradiation, the anisotropicliquid crystal material comprising an alkenyl compound which is stableto the polymerization reaction during the polymerization of thepolymerizable monomers, the molar ratio between the two polymerizablemonomers in the mixture for liquid crystal medium being 1:5, the weightpercentage of the polymerizable monomers accounting for 0.1% to 1% ofthe total mixture for liquid crystal medium; the structural formulas ofthe anisotropic liquid crystal material being selected from thefollowing structural formulas:

wherein, R represents the straight chain or branched chain alkylcontaining number of carbon atoms from 1 to 9, one or more non-adjacentmethyl groups or methylene groups of the alkyl may be replaced by oxygenor sulfur atom; the weight percentage of the anisotropic liquid crystalmaterial accounts for 20% to 90% of the total mixture for the liquidcrystal medium; the structural formulas of the two polymerizablemonomers defined by the following structural formula, the number ofgroups is different when the structural formulas of the twopolymerizable monomers are the same:

wherein, in formula IV, P represents the polymerizable group, which isselected from the group consisting of a methacrylate group, an acrylategroup, a vinyl group, an ethylene group, and an epoxy group; nrepresents the number of the polymerizable groups Ps connected to thesame aromatic ring, n represents an integer from 1 to 3, if n is greaterthan 1, the polymerizable groups may be the same or different; Xrepresents substituent group, which is selected from the groupconsisting of —F, —Cl, —Br, methyl, —CN, and straight chain or branchedchain alkyl containing number of carbon atoms from 2 to 8, one or morenon-adjacent methyl groups of the alkyl may be replaced by oxygen orsulfur atom; m represents the number of the substituent groups connectedto the same aromatic ring, m represents an integer from 1 to 3, if m isgreater than 1, the substituent groups may be the same or different; informula IV, Z is selected from the group consisting of —O—, —COO—,—OCO—, —CH₂O—, —OCH₂O—, —O(CH₂)₂O, —COCH₂—, methylene, —C≡C—,


2. The mixture for liquid crystal medium as claimed in claim 1,characterized in that any hydrogen on the aromatic ring in thestructural formulas of the polymerizable monomer may be substituted bythe group of —F, —Cl, —Br, methyl or —CN.
 3. The mixture for liquidcrystal medium as claimed in claim 1, characterized in that any hydrogennot on the aromatic ring in the structural formulas of the polymerizablemonomer may be substituted by the group of —F, —C, —Br or methyl.
 4. Aliquid crystal display comprising: a upper substrate and a lowersubstrate which are parallel with each other, and a mixture for liquidcrystal medium provided between the upper substrate and the lowersubstrate, the mixture for liquid crystal medium comprising: at leastone anisotropic liquid crystal material and two polymerizable monomerswhich will polymerize under UV irradiation, the anisotropic liquidcrystal material comprising an alkenyl compound which is stable to thepolymerization reaction during the polymerization of the polymerizablemonomers, the molar ratio of between the two polymerizable monomers inthe mixture for liquid crystal medium being 1:5, the weight percentageof the polymerizable monomers accounting for 0.1% to 1% of the totalmixture for liquid crystal medium; the structural formulas of theanisotropic liquid crystal material being selected from the followingstructural formulas:

wherein, R represents the straight chain or branched chain alkylcontaining number of carbon atoms from 1 to 9, one or more non-adjacentmethyl groups or methylene groups of the alkyl may be replaced by oxygenor sulfur atom; the weight percentage of the anisotropic liquid crystalmaterial accounts for 20% to 90% of the total mixture for the liquidcrystal medium; the structural formulas of the two polymerizablemonomers defined by the following structural formula, the number ofgroups is different when the structural formulas of the twopolymerizable monomers are the same:

wherein, in formula IV, P represents the polymerizable group, which isselected from the group consisting of a methacrylate group, an acrylategroup, a vinyl group, an ethylene group, and an epoxy group; nrepresents the number of the polymerizable groups Ps connected to thesame aromatic ring, n represents an integer from 1 to 3, if n is greaterthan 1, the polymerizable groups may be the same or different; Xrepresents substituent group, which is selected from the groupconsisting of —F, —Cl, —Br, methyl, —CN, and straight chain or branchedchain alkyl containing number of carbon atoms from 2 to 8, one or morenon-adjacent methyl groups of the alkyl may be replaced by oxygen orsulfur atom; m represents the number of the substituent groups connectedto the same aromatic ring, m represents an integer from 1 to 3, if m isgreater than 1, the substituent groups may be the same or different; informula IV, Z is selected from the group consisting of —O—, —COO—,—OCO—, —CH₂O—, —OCH₂O—, —O(CH₂)₂O—, —COCH₂—, methylene, —C≡C—,


5. The liquid crystal display as claimed in claim 4, characterized inthat any hydrogen on the aromatic ring in the structural formulas of thepolymerizable monomer may be substituted by the group of —F, —Cl, —Br,methyl or —CN.
 6. The liquid crystal display as claimed in claim 4,characterized in that any hydrogen not on the aromatic ring in thestructural formulas of the polymerizable monomer may be substituted bythe group of —F, —Cl, —Br or methyl.